CN100450365C - Hydroxyl apatite inorganic antibacterial agent containing silver and zinc ions - Google Patents

Hydroxyl apatite inorganic antibacterial agent containing silver and zinc ions Download PDF

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CN100450365C
CN100450365C CNB2004100496535A CN200410049653A CN100450365C CN 100450365 C CN100450365 C CN 100450365C CN B2004100496535 A CNB2004100496535 A CN B2004100496535A CN 200410049653 A CN200410049653 A CN 200410049653A CN 100450365 C CN100450365 C CN 100450365C
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hydroxyapatite
antibacterial agent
inorganic antiseptic
zinc
argentiferous
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CN1711847A (en
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王岩
杨淑琴
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SHENGXINZE REAL ESTATE CO Ltd BEIJING
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SHENGXINZE REAL ESTATE CO Ltd BEIJING
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Abstract

The present invention relates to a hydroxyapatite inorganic antibacterial agent containing silver ion and zinc ion. The inorganic antibacterial agent takes hydroxyapatite as carriers. The present invention is characterized in that the inorganic antibacterial agent adopts the main raw materials and the dosage of 60 to 70 weight shares of Ca (OH) 2, 40 to 50 weight shares of H3PO4, 1 to 3 weight shares of AgNO3, and 4 to 6 weight shares of Zn (NO3) 2. The auxiliary materials are ammonia water and zinc-magnesium oxide solid solution. The chemical molecular formula of the hydroxyapatite is Ca10 (PO4) 6 (OH) 2. The chemical composition of the inorganic antibacterial agent is Ag-Zn-Ca10 (PO4) 6 (OH) 2. The present invention has the preparation procedure that (1) the Ca (OH) 2 is dissolved; (2) the hydroxyapatite is deposited; (3) all materials are heated and stirred; (4) reaction solution is checked; (5) the reaction solution is filtered, washed by water and dried; (6) the antibacterial agent is prepared by ion exchange; (7) the antibacterial agent is processed by discoloration resistance; (8) the antibacterial agent is tested; (9) the inorganic antibacterial agent is made into finished products. The present invention combines zinc-magnesium oxide solid solution antibacterial materials with silver-zinc-hydroxyapatite inorganic antibacterial agents so that the present invention has the advantages of high antibacterial efficiency, low cost and economic usefulness.

Description

The hydroxyapatite inorganic antiseptic and the manufacture method thereof of argentiferous, zinc ion
Technical field
The present invention relates to a kind of inorganic antiseptic and manufacture method thereof, particularly a kind of bacteriostasis rate height, the argentiferous that cost is low, the hydroxyapatite inorganic antiseptic and the manufacture method thereof of zinc ion.
Background technology
Fast development along with China's economic construction; the raising of living standards of the people; people are to the quality of life, the protection and the healthy attention more of environment; the invasion and attack of SARS (Severe Acute Respiratory Syndrome) and the test of avian influenza virus have particularly been experienced; the construction of raising and reinforcement public environment sanitary installation is extremely urgent; how to reduce the probability that high density crowd large tracts of land breaks out pernicious infectious disease effectively, diseases prevention, the epidemic prevention level that improves people is the important topic of pendulum in face of government, medical personnel and scientific research personnel.
At present, the extensive use of inorganic antimildew and antibacterial agent is the important symbol that living standards of the people improve, the antimicrobial product that has added antibacterial agent can make household appliances, amenities, medical supplies, the facility of public place and ornament materials, packaging material are disease carrying germ not, virus, stop germina infection, reduce the incidence of disease of infectious disease, improve the people's the general level of the health, but, because the carrier cost height of existing antimicrobial product, enterprise investment is big, and extensive use is limited to, technically, its high temperature fastness processing can cause antimicrobial efficiency not high, and remaining further, research improves.
In view of this, in order to overcome above-mentioned shortcoming, this creator is according to oneself practical experience and technical concept, after deliberation, test, and has the present invention to produce eventually.
Summary of the invention
The present invention is hydroxyapatite inorganic antiseptic and the manufacture method thereof that a kind of argentiferous, zinc ion will be provided, and makes its tool bacteriostasis rate height, fastness and the low technical problem of cost with solution.
It is such solving the problems of the technologies described above the technical scheme that is adopted:
The hydroxyapatite inorganic antiseptic of a kind of argentiferous, zinc ion, this inorganic antiseptic are to be carrier with the hydroxyapatite, and it is characterized in that: the main raw material(s) composition and the consumption of this inorganic antiseptic are:
Ca (OH) 260～70 weight portions; H 3PO 440～50 weight portions;
AgNO 31～3 weight portion; Zn (NO 3) 24～6 weight portions;
Auxiliary material is ammoniacal liquor and zinc-magnesium oxide solid solution;
The chemical molecular formula of this hydroxyapatite is Ca 10(PO 4) 6(OH) 2
The chemical composition of the hydroxyapatite inorganic antiseptic of this argentiferous, zinc ion is:
Ag-Zn-Ca 10(PO 4) 6(OH) 2。
The manufacture method of the hydroxyapatite inorganic antiseptic of a kind of argentiferous, zinc ion is characterized in that, the flow process of this manufacture method is:
(1) Ca (OH) 2Dissolving: Ca (OH) 2Transfer to molten entirely with inorganic acid;
(2) precipitation hydroxyapatite: this Ca (OH) 2Add H in the solution 3PO 4Mix, under 80～100 ℃ of conditions, react 5～8 hours generation hydroxyapatite Ca 10(PO 4) 6(OH) 2, its chemical equation is as follows:
10Ca(OH) 2+6H 3PO 4→Ca 10(PO 4) 6(OH) 2↓+18H 2O
In the above-mentioned course of reaction, because Ca (OH) 2Dissolving must under acid condition, carry out, and hydroxyapatite only could generate separately under the highly basic condition, so H in the course of reaction 3PO 4With ammoniacal liquor reaction solution is transferred to pH＞10;
(3) intensification is stirred: after reaction is finished, be warmed up to 80～120 ℃ and continue to stir, drop to neutrality (pH ≈ 7) until the pH of reactant liquor;
(4) reaction solution inspection: use AgNO 3Solution is checked the phosphate radical in the reaction solution, stops when not having phosphate radical in the reaction solution stirring;
(5) filtration, washing, drying: when temperature drops to normal temperature, filter, wash, drying, generate nano level hydroxylapatite powder (HA powder);
(6) antibacterial agent is made in ion exchange: with hydroxylapatite powder at AgNO 3And Zn (NO 3) 2The aqueous solution in carry out ion exchange, the condition during ion exchange is: AgNO 3Weight portion be 1～3% of HA, Zn (NO 3) 2Weight portion be 4～6% of HA, the exchange temperature is 80～100 ℃, the time is 12 hours, generates the hydroxyapatite inorganic antiseptic of argentiferous, zinc ion;
(7) fastness is handled: comprise the processing of fastness high temperature treatment and fastness light shield, wherein, the fastness high temperature treatment is to adopt 1200 ℃ of high temperature treatment of heating 2 hours; It is to adopt a kind of oxide solid solution to make photomask agent that the fastness light shield is handled, to contain Ag, the Zn inorganic antiseptic is made the fastness light shield and is handled, thereby prevent to contain the variable color trend of inorganic antiseptic under illumination condition of Ag, Zn;
(8) antibacterial agent check: the anti-microbial property of antibacterial agent detects, and mainly by staphylococcus aureus and colibacillary bacteriostasis rate are detected anti-microbial property, requires poor＞26% of bacteriostasis rate;
(9) inorganic antiseptic finished product: by the qualified products of above-mentioned technological process making, check;
This nano level hydroxyapatite powder dimensions length is less than 10nm, width ≈ 30nm;
This oxide solid solution is zinc-magnesium oxide solid solution;
Should be 1000～1200 orders in order to the filter cloth that filters.
Silver of the present invention, the hydroxyapatite inorganic antiseptic of zinc ion, adopt zinc-magnesium oxide solid solution anti-biotic material to combine with silver-zinc-hydroxyapatite inorganic antiseptic, suppress silver-zinc inorganic antiseptic and met heat, meet the trend of phototropic, adopt this technology than adopting the high-temperature processing technology anti-microbial property to significantly improve, with silver, zinc ion is main active sterilization component, with the carrier of hydroxyapatite as the antibacterial activity composition, its hydroxyapatite is the basic composition thing of skeleton, has very good compatibility with human body, human body there is not any toxicity, environmentally safe, because one of special performance of hydroxyapatite is that the absorption of wide spectrum and the effect of concentrated bacterium are arranged, being convenient to metal ion suppresses and kill bacteria, again because hydroxyapatite has good ion-exchange capacity, form the antibacterial agent of wide spectrum, suppress and kill virus, germ, again because hydroxyapatite has high stability, high to more than 1000 ℃ or not phase transformation of higher temperature, the antibacterial agent of making is higher than zeolite etc. to photo and thermal stability, its antitoxin efficient height and cost are low, make its tool bacteriostasis rate height thereby solved, the technical problem that fastness and cost are low.
Bacteriostasis rate height of the present invention, cost are low, and manufacture method is easy, and its advantage is as follows:
1, the present invention adopts the carrier of hydroxyapatite as the antibacterial activity composition, because hydroxyapatite is nontoxic, to the human body nonhazardous, it is safe.
2, the present invention adopts zinc-magnesium oxide solid solution anti-biotic material to combine with silver-zinc-hydroxyapatite inorganic antiseptic, suppressed the trend that silver-zinc inorganic antiseptic is met heat, met phototropic, tool broad spectrum antibacterial, fastness, antimicrobial efficiency height, long characteristics of life-span.
3, the present invention has the collaborative antibacterial characteristics of metal ion and active oxygen concurrently, its antimicrobial efficiency height and cost is low, the tool economic and practical.
4, the present invention is high temperature resistant durable in use, joins in pottery, plastics, fiber and the coating, can be made into anti-bacteria ceramic, antibiotic plastic, antibiotic clothing, antibiotic paper, antibiotic paint, applied range.
Description of drawings
Fig. 1 is a manufacturing process flow diagram of the present invention.
Embodiment
As shown in Figure 1, be process for making flow chart of the present invention, the hydroxyapatite inorganic antiseptic of this argentiferous, zinc ion is to be carrier with the hydroxyapatite, and wherein, the main raw material(s) composition and the consumption of this inorganic antiseptic are:
Ca (OH) 260～70 weight portions; H 3PO 440～50 weight portions;
AgNO 31～3 weight portion; Zn (NO 3) 24～6 weight portions;
Auxiliary material is ammoniacal liquor and zinc-magnesium oxide solid solution;
The chemical molecular formula of this hydroxyapatite is Ca 10(PO 4) 6(OH) 2
The chemical composition of the hydroxyapatite inorganic antiseptic of this argentiferous, zinc ion is:
Ag-Zn-Ca 10(PO 4) 6(OH) 2。
The manufacture method of the hydroxyapatite inorganic antiseptic of a kind of argentiferous, zinc ion is:
(1) Ca (OH) 2Dissolving: Ca (OH) 2Transfer to molten entirely with inorganic acid;
(2) precipitation hydroxyapatite: this Ca (OH) 2Add H in the solution 3PO 4Mix, under 80～100 ℃ of conditions, react 5～8 hours generation hydroxyapatite Ca 10(PO 4) 6(OH) 2, its chemical equation is as follows:
10Ca(OH) 2+6H 3PO 4→Ca 10(PO 4) 6(OH) 2↓+18H 2O
In the above-mentioned course of reaction, because Ca (OH) 2Dissolving must under acid condition, carry out, and hydroxyapatite only could generate separately under the highly basic condition, so H in the course of reaction 3PO 4With ammoniacal liquor reaction solution is transferred to pH＞10;
(3) intensification is stirred: after reaction is finished, be warmed up to 80～120 ℃ and continue to stir, drop to neutrality (pH ≈ 7) until the pH of reactant liquor;
(4) reaction solution inspection: use AgNO 3Solution is checked the phosphate radical in the reaction solution, stops when not having phosphate radical in the reaction solution stirring;
(5) filtration, washing, drying: when temperature drops to normal temperature, filter, wash, drying, generate nano level hydroxylapatite powder (HA powder), this nano level hydroxyapatite powder dimensions length is less than 10nm, and width ≈ 30nm should be 1000～1200 orders in order to the filter cloth that filters;
(6) antibacterial agent is made in ion exchange: with hydroxylapatite powder at AgNO 3And Zn (NO 3) 2The aqueous solution in carry out ion exchange, the condition during ion exchange is: AgNO 3Weight portion be 1～3% of HA, Zn (NO 3) 2Weight portion be 4～6% of HA, the exchange temperature is 80～100 ℃, the time is 12 hours, generates the hydroxyapatite inorganic antiseptic of argentiferous, zinc ion;
(7) fastness is handled: comprise the processing of fastness high temperature treatment and fastness light shield, wherein, the fastness high temperature treatment is to adopt 1200 ℃ of high temperature treatment of heating 2 hours; The fastness light shield handle be adopt zinc-magnesium oxide solid solution to contain Ag, the Zn inorganic antiseptic is made the fastness light shield and is handled, thereby prevent to contain the variable color trend of inorganic antiseptic under illumination condition of Ag, Zn;
(8) antibacterial agent check: the anti-microbial property of antibacterial agent detects, and mainly by staphylococcus aureus and colibacillary bacteriostasis rate are detected anti-microbial property, requires poor＞26% of bacteriostasis rate;
(9) inorganic antiseptic finished product: by the qualified products of above-mentioned technological process making, check.
The anti-microbial property test result of the hydroxyapatite inorganic antiseptic of this argentiferous, zinc ion sees Table 1 and table 2.
The antibiotic rate of the hydroxyapatite inorganic antiseptic of table 1 argentiferous, zinc ion
Figure C20041004965300081
The comparison of the antibacterial effect bacteriostasis rate of the similar antibacterial agent of table 2
Figure C20041004965300082
By above contrast as can be seen, 2 hours the fungistatic effect of hydroxyapatite inorganic antiseptic of this argentiferous, zinc ion is suitable with external 24 hours fungistatic effect of contrast product.
Application test of the present invention shows: the hydroxyapatite inorganic antiseptic of this argentiferous, zinc ion adds in the enamel through 1280 ℃ and burns till anti-bacteria ceramic, and its ceramic bacteriostasis rate reaches more than 90%; Whole interior walls and experiment cabinet inwall in the aseptic experiment chamber add in the coating with antibacterial agent of the present invention, and whitewashing back interior wall and experiment cabinet does not have mould to take place.
In sum, effect of the present invention has tangible lifting, and the tool economic and practical meets each important document of patent of invention, so propose application for a patent for invention in accordance with the law.

Claims (4)

1, the hydroxyapatite inorganic antiseptic of a kind of argentiferous, zinc ion, this inorganic antiseptic is to be carrier with the hydroxyapatite, it is characterized in that: the main raw material(s) composition and the consumption of this inorganic antiseptic are:
Ca (OH) 260～70 weight portions; H 3PO 440～50 weight portions;
AgNO 31～3 weight portion; Zn (NO 3) 24～6 weight portions;
Auxiliary material is ammoniacal liquor and zinc-magnesium oxide solid solution;
The chemical molecular formula of this hydroxyapatite is Ca 10(PO 4) 6(OH) 2
The chemical composition of the hydroxyapatite inorganic antiseptic of this argentiferous, zinc ion is:
Ag-Zn-Ca 10(PO 4) 6(OH) 2。
2, the manufacture method of the hydroxyapatite inorganic antiseptic of a kind of argentiferous, zinc ion is characterized in that, the flow process of this manufacture method is:
(1) Ca (OH) 2Dissolving: Ca (OH) 2Transfer to molten entirely with inorganic acid;
(2) precipitation hydroxyapatite: this Ca (OH) 2Add H in the solution 3PO 4Mix, under 80～100 ℃ of conditions, react 5～8 hours generation hydroxyapatite Ca 10(PO 4) 6(OH) 2, its chemical equation is as follows:
10Ca(OH) 2+6H 3PO 4→Ca 10(PO 4) 6(OH) 2↓+18H 2O
H in the course of reaction 3PO 4With ammoniacal liquor reaction solution is transferred to pH＞10;
(3) intensification is stirred: after reaction is finished, be warmed up to 80～120 ℃ and continue to stir, drop to neutrality until the pH of reactant liquor;
(4) reaction solution inspection: use AgNO 3Solution is checked the phosphate radical in the reaction solution, stops when not having phosphate radical in the reaction solution stirring;
(5) filtration, washing, drying: when temperature drops to normal temperature, filter, wash, drying, generate nano level hydroxylapatite powder;
(6) antibacterial agent is made in ion exchange: with hydroxylapatite powder at AgNO 3And Zn (NO 3) 2The aqueous solution in carry out ion exchange, the condition during ion exchange is: AgNO 3Weight portion be 1～3% of hydroxylapatite powder, Zn (NO 3) 2Weight portion be 4～6% of hydroxylapatite powder, the exchange temperature is 80～100 ℃, the time is 12 hours, generates the hydroxyapatite inorganic antiseptic of argentiferous, zinc ion;
(7) fastness is handled: comprise the processing of fastness high temperature treatment and fastness light shield, wherein, the fastness high temperature treatment is to adopt 1200 ℃ of high temperature treatment of heating 2 hours; It is to adopt a kind of zinc-magnesium oxide solid solution to make photomask agent that the fastness light shield is handled, to contain Ag, the Zn inorganic antiseptic is made the fastness light shield and is handled;
(8) antibacterial agent check: the anti-microbial property of antibacterial agent detects, and mainly by staphylococcus aureus and colibacillary bacteriostasis rate are detected anti-microbial property, requires poor＞26% of bacteriostasis rate;
(9) inorganic antiseptic finished product: by the qualified products of above-mentioned technological process making, check.
3, the manufacture method of the hydroxyapatite inorganic antiseptic of argentiferous according to claim 2, zinc ion is characterized in that: this nano level hydroxyapatite powder dimensions length is less than 10nm, width ≈ 30nm.
4, the manufacture method of the hydroxyapatite inorganic antiseptic of argentiferous according to claim 2, zinc ion is characterized in that: should be 1000～1200 orders in order to the filter cloth that filters.
CNB2004100496535A 2004-06-23 2004-06-23 Hydroxyl apatite inorganic antibacterial agent containing silver and zinc ions Expired - Fee Related CN100450365C (en)

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CN101327340B (en) * 2008-07-11 2012-09-05 西安交通大学 Method for preparing bacterial inhibition-resistance petal-shaped or sheet-shaped Ag/Cu/HAP nano compound powder
CN102845471B (en) * 2012-07-27 2014-04-30 烟台大学 Silver-based composite particle, preparation method of the silver-based composite particle and antibacterial agent containing the silver-based composite particle
TW201442945A (en) * 2013-05-08 2014-11-16 wen-li Zhang Method of utilizing fish scale powder to prepare antibacterial, odorless and collagen-containing Hydroxy-Apatite and its finished product
CN105297402A (en) * 2015-10-16 2016-02-03 上海纳米技术及应用国家工程研究中心有限公司 Preparation method for growing hydroxyapatite on surface of hydrophobic fiber
CN107281555B (en) * 2017-06-22 2020-09-29 江苏沥泽生化科技有限公司 Preparation method of silver-loaded nano hydroxyapatite with strong effect, long-acting and antibacterial effects and product thereof
CN108187136A (en) * 2017-12-29 2018-06-22 连云港碳谷材料科技有限公司 A kind of preparation method of nanometer of load zinc hydroxyapatite
CN111509307B (en) * 2020-04-22 2023-08-15 中南大学 Preparation method and application of inorganic colloid electrolyte of water-based zinc ion battery
CN112620626B (en) * 2020-11-24 2022-01-28 淮阴工学院 Forming method of bone induction type titanium alloy bone implant with high antibacterial property
CN112409871A (en) * 2020-11-30 2021-02-26 成都新柯力化工科技有限公司 Antibacterial polymer-based waterproof coating and preparation method thereof

Citations (3)

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Publication number Priority date Publication date Assignee Title
CN1402989A (en) * 2002-09-12 2003-03-19 中国科学院广州地球化学研究所 Delay-released inorganic nano antiseptic with high whiteness and its prepn
CN1402988A (en) * 2002-09-12 2003-03-19 中国科学院广州地球化学研究所 Needle inorganic nano antiseptic with great length-diameter ratio and its prepn
CN1426683A (en) * 2001-12-17 2003-07-02 北京有色金属研究总院 High temp. resistant, colour fastness inorganic antimicrobial mildew preventive agent and its preparing method

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1426683A (en) * 2001-12-17 2003-07-02 北京有色金属研究总院 High temp. resistant, colour fastness inorganic antimicrobial mildew preventive agent and its preparing method
CN1402989A (en) * 2002-09-12 2003-03-19 中国科学院广州地球化学研究所 Delay-released inorganic nano antiseptic with high whiteness and its prepn
CN1402988A (en) * 2002-09-12 2003-03-19 中国科学院广州地球化学研究所 Needle inorganic nano antiseptic with great length-diameter ratio and its prepn

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